EP3602020B1 - Procédé de réalisation d'une spectroscopie des rayons x et système de spectromètre d'absorption de rayons x - Google Patents

Procédé de réalisation d'une spectroscopie des rayons x et système de spectromètre d'absorption de rayons x Download PDF

Info

Publication number
EP3602020B1
EP3602020B1 EP18771876.2A EP18771876A EP3602020B1 EP 3602020 B1 EP3602020 B1 EP 3602020B1 EP 18771876 A EP18771876 A EP 18771876A EP 3602020 B1 EP3602020 B1 EP 3602020B1
Authority
EP
European Patent Office
Prior art keywords
ray
crystal
rays
energy
absorption spectrum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18771876.2A
Other languages
German (de)
English (en)
Other versions
EP3602020A1 (fr
EP3602020A4 (fr
Inventor
Wenbing Yun
Sylvia Jia Yun Lewis
Janos KIRZ
Srivatsan Seshadri
Alan Francis Lyon
Benjamin Donald Stripe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sigray Inc
Original Assignee
Sigray Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sigray Inc filed Critical Sigray Inc
Priority claimed from PCT/US2018/023547 external-priority patent/WO2018175570A1/fr
Publication of EP3602020A1 publication Critical patent/EP3602020A1/fr
Publication of EP3602020A4 publication Critical patent/EP3602020A4/fr
Application granted granted Critical
Publication of EP3602020B1 publication Critical patent/EP3602020B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
    • G01N23/06—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption
    • G01N23/083—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption the radiation being X-rays
    • G01N23/085—X-ray absorption fine structure [XAFS], e.g. extended XAFS [EXAFS]
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
    • G21K1/06—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J35/00—X-ray tubes
    • H01J35/02—Details
    • H01J35/04—Electrodes ; Mutual position thereof; Constructional adaptations therefor
    • H01J35/08—Anodes; Anti cathodes
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K2201/00—Arrangements for handling radiation or particles
    • G21K2201/06—Arrangements for handling radiation or particles using diffractive, refractive or reflecting elements
    • G21K2201/062—Arrangements for handling radiation or particles using diffractive, refractive or reflecting elements the element being a crystal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2235/00—X-ray tubes
    • H01J2235/08—Targets (anodes) and X-ray converters
    • H01J2235/086—Target geometry
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2235/00—X-ray tubes
    • H01J2235/12—Cooling
    • H01J2235/1225—Cooling characterised by method
    • H01J2235/1291—Thermal conductivity

Definitions

  • the embodiments of the invention disclosed herein relate to a method performing x-ray spectroscopy and an x-ray spectrometry systems having an x-ray illumination system comprising a focusing x-ray optic with an energy bandwidth greater than 10 eV that collects x-rays from the laboratory source and focuses portion of the collected x-rays on or near an object with a focus size less than 500 micrometers.
  • the focus spot is ⁇ 10-20 um.
  • Various embodiments of the spectrometer may have a variety of x-ray materials and optical elements to provide a variety of x-ray bandwidth ranges suitable for a variety of x-ray spectroscopy applications.
  • X-ray absorption spectroscopy is a technique commonly employed at high brightness synchrotron light sources for chemical analysis, but has been limited in its application at the laboratory due to a combination of the long acquisition times needed and poor spectral resolution of laboratory systems. To this end, a laboratory XAS system is described with significant innovations to increase the flux of x-rays at specific energies and achieve high spectral resolution to would allow better analysis of the absorption fine structure associated with the absorption edge.
  • x-rays are created by bombarding an anode target having a selected x-ray generating material with electrons accelerated through a potential (measured in keV) in a vacuum. With the collision of the electrons and the material, there are several energy transfer mechanisms that can occur, including heat and the generation of x-rays.
  • a spectrum of x-rays is produced with x-ray energies up to the original electron energy (in this example, about 50 KeV) which includes characteristic x-rays and continuum, often referred to as Bremsstrahlung radiation.
  • Ways to increase the brightness of the x-ray source is to increase the energy of the electrons by raising the accelerating voltage, use a target material with a higher atomic number Z, and/or to increase the electron density bombarding the material.
  • this is generally limited by the ability of the material to absorb energy without melting or damage. Therefore, most current art electron bombardment x-ray sources comprise a single x-ray radiating material with good thermal properties, such as a high melting point and high thermal conductivity.
  • the target material may also be mounted onto, or embedded into, a substrate having properties selected to efficiently conduct heat away from the x-ray generating material, with the thickness of the x-ray generating material limited by the electron penetration depth.
  • X-rays generated by electron beam bombardment generally radiate in all directions and x-ray flux density on a sample for a given analysis area can be increased through the use of optics.
  • the focusing optic needs to work for an energy bandwidth.
  • x-ray optics have generally not used and instead a microfocus x-ray source is used.
  • X-ray absorption spectroscopy typically measures the fraction of x-rays absorbed by an object as a function of x-ray energy over a predetermined energy range with energy resolution better than 10 eV, inclusive an absorption edge of an element in the object. It is often carried out at synchrotron light sources because of their high brightness and easy energy tunability. Small laboratory-based x-ray absorption spectroscopy systems would provide easy access and full control; however the performance of laboratory XAS systems has been largely limited by a combination of many factors, including low brightness of the Bremsstrahlung radiation of laboratory x-ray sources, low diffraction efficiency of the crystal analyzer associated with the use of high index reflections, and non-optimal spectrometer design. Those limitations often result in unacceptably long acquisition times ( ⁇ up to tens of hours) and/or poor energy resolution. As a consequence, there are few laboratory systems in use.
  • crystal analyzers need to operate at high Bragg angles to achieve adequate energy resolution; because x-ray energy range for a crystal analyzer operating at high Bragg angles is typically limited to a narrow operating energy range, a large number of crystal analyzers are required for the spectrometer to operate over a sufficiently wide energy bandwidth; because a crystal analyzer operating at high Bragg angles typically reflects an energy bandwidth significantly narrower than the energy resolution required for XAS measurement, it leads to significant loss in measurement throughput. Additionally, XAS measurement is typically performed by scanning x-ray energy point by point.
  • x-ray absorption spectroscopy measurement and an x-ray absorption spectrometer to measure x-ray transmission with high throughput, high spatial, and high spectral resolution.
  • the disclosed x-ray absorption spectrometer comprises a laboratory x-ray source, and an optical train which focuses x-rays over an energy bandwidth greater than 10 eV emerging from the x-ray source on or near an object to be examined with an focus size less than 500 micrometers.
  • the benefits of the optical train include high x-ray flux on the sample and small illuminated spot for analyzing a small area (high spatial resolution) and use of crystal analyzers with low Bragg angles for high throughput, and compactness of the spectrometer. Additionally, it may also serves as a low-pass filter with a predetermined high-energy cut-off for the x-rays.
  • the benefit of using an optical train that has properties enabling it to serve as low-pass focusing reflector is that the x-ray production efficiency of the x-ray source can be increased by enabling the energy of the bombarding electrons in the x-ray source to be substantially higher.
  • the x-ray optical elements in the train may comprise capillary x-ray optics, including reflecting surface profiles that correspond to one or more portions of quadric functions such as paraboloids, ellipsoids, or Wolter-type (e.g. paraboloidal and hyperboloidal profiles).
  • Optical elements include but are not limited to x-ray mirror optics based on total external reflection. For an x-ray of incident at an angle ⁇ onto a surface of a material with atomic number Z, the reflectivity is nearly 100% for near-grazing angles (e.g. ⁇ ⁇ 0o), and falls off for angles larger than a material-dependent and x-ray energy dependent critical angle ⁇ c . Critical angles are typically smaller than 2°, limiting the acceptance angle for most x-ray optical systems.
  • focusing multilayer optics such as Montel Optics may be used.
  • the higher brightness compact x-ray source is achieved in part through the use of novel x-ray targets used in generating x-rays from electron beam bombardment.
  • These x-ray target configurations may comprise a number of microstructures of one or more selected x-ray generating materials fabricated in close thermal contact with (such as embedded in or buried in) a substrate with high thermal conductivity, such that the heat is more efficiently removed from the x-ray generating material. This in turn allows bombardment of the x-ray generating material with higher electron density and/or higher energy electrons, which leads to greater x-ray brightness and greater x-ray flux.
  • An object to be examined is placed in the path of the focused x-ray beam, and an aperture may be placed at or near the point of focus to selectively pass the transmitted x-rays while restricting the widely radiated x-ray fluorescence.
  • the object may be translated in the plane perpendicular with respect to the x-ray beam to allow 2-D "map" of the transmitted spectrum to be collected or rotated about its axis with or without translation so that 3D tomography of the transmission spectrum can be collected.
  • the x-ray absorption spectroscopy system comprises also at least one spatially resolved x-ray detector.
  • the crystal analyzer is positioned to receive and diffract the x-rays transmitting through the object onto an spatially resolving detector, aligned so that different pixels of the detector correspond to different x-ray wavelengths.
  • FIGURE 1 illustrates an embodiment of an x-ray spectrometer system 200 comprising an x-ray source 80, an x-ray optical system 3000 that includes an object 240 to be examined by x-ray transmission, also referred to as a sample by those skilled in the art, a spectrometer 3700 comprising a detector 290 and a crystal 291, and signal processing electronics 292 and an analysis system 295 with a display 298.
  • the object 240 to be examined will also be referred to as the sample hereinafter.
  • the source 80 comprises a vacuum environment (typically 1.333 10 -6 mbar (10 -6 Torr) or better) commonly maintained by a sealed vacuum chamber 20 or active pumping, and manufactured with sealed electrical leads 21 and 22 that pass from the negative and positive terminals of a high voltage source 10 outside the tube to the various elements inside the vacuum chamber 20.
  • the source 80 will typically comprise mounts 30 which secure the vacuum chamber 20 in a housing 50, and the housing 50 may additionally comprise shielding material, such as lead, to prevent x-rays from being radiated by the source 80 in unwanted directions.
  • an electron emitter 11 connected through the lead 21 to the negative terminal of a high voltage source 10, which serves as a cathode and generates a beam of electrons 111.
  • a high voltage source 10 which serves as a cathode and generates a beam of electrons 111.
  • Any number of prior art techniques for electron beam generation may be used for the embodiments of the invention disclosed herein, such as thermionic emission, field emission, Schottky emission, emitters comprising nanostructures such as carbon nanotubes), and by use of ferroelectric materials.
  • a target 1100 comprising a target substrate 1000 and one or more x-ray generating structure(s) 700 comprising one or more x-ray generating materials is electrically connected to the opposite high voltage lead 22 and target support 32 to be at ground or a positive voltage relative to the electron emitter 11, thus serving as an anode.
  • the electrons 111 accelerate towards the target 1100 and collide with it at high energy, with the energy of the electrons determined by the magnitude of the accelerating voltage.
  • the collision of the electrons 111 into the target 1100 induces several effects, including the radiation of x-rays 888, some of which exit the vacuum chamber 20 and are transmitted through a window 40 transmissive to x-rays.
  • an electron control mechanism 70 such as an electrostatic lens system or other system of electron optics that is controlled and coordinated with the electron dose and voltage provided by the electron emitter 11 by a controller 10-1 through an additional lead 27.
  • the electron beam 111 may therefore be scanned, focused, de-focused, or otherwise directed onto target 1100 comprising one or more x-ray generating structures 700 fabricated to be in close thermal contact with a substrate 1000.
  • optical system 3000 typically comprising one or more optical trains 840.
  • the optical trains comprise x-ray optical elements with axial symmetry such as capillary optics.
  • the elements of the optical train 840 reflect x-rays at grazing angles to focus a portion 887 of the x-rays onto a focal spot.
  • an aperture component 270 having one or more apertures 272 is coincident with the focal spot.
  • the object 240 to be examined is typically placed in a mount 244 and positioned just before the aperture 272.
  • the mount may allow the object 240 to be translated and/or rotated so that different portions of the object 240 are illuminated by the converging x-rays 887, allowing different positions on the object 240 to be illuminated in a systematic scan or from several angles of incidence, with this motion controlled by a controller 246.
  • X-rays propagating along the axis of the optical train that are not collected and focused may be blocked by a beam stop 850.
  • the transmitted x-rays 888-T are collected by a spectrometer 3700.
  • the spectrometer 3700 typically comprises at least one dispersing x-ray crystal 291 and an x-ray detector 290. In some instances, the distance between the apparent source of x-rays on the sample and the at least one analyzer crystal is less than two (2) meters.
  • the detector 290 will typically be an array detector, positioned to record the intensity of the dispersed x-rays as a function of position. Additional signal processing electronics 292 and analysis system 295 correlate the intensity signals to the corresponding x-ray energy.
  • the analysis system 295 may additionally comprise a display 298.
  • the detector 290 may also comprise sensors and electronics that serve as an x-ray spectrometer, analyzing both the number of x-ray fluorescence photons emerging from the object 240 as well as their energy.
  • An x-ray optical train is placed downstream of the x-ray source to collect and focus a portion of the x-rays generated by the x-ray source.
  • the x-ray optic has a cut-off energy above which x-ray reflection is reduced to 30% or less. The use of this optic enables the operation of the x-ray source at higher accelerating voltages that significantly increase efficient generation of bremsstrahlung radiation.
  • laboratory x-ray sources have been limited to operation of less than 2X the characteristic energy of interest of the element under examination, because of potential contamination from multiple order diffraction.
  • the x-ray optical train comprises at least one capillary x-ray optic with an inner surface profile that corresponds one or more portions of a quadric function, such as an ellipsoid, paraboloid, or a Wolter-type (paraboloid and ellipsoid/hyperboloid).
  • the x-ray optic may be a Montel mirror or other x-ray optics known to those versed in the art.
  • the optic may be coated with a coating such as a multilayer coating or a high atomic element (e.g. atomic number greater than 26) or alloy, such as Platinum.
  • the focal point of the x-ray optical train serves as a secondary source for a spectrometer comprising one or more crystals.
  • spectrometers are described herein and comprise at least one x-ray crystal and one x-ray detector.
  • the x-ray source 80 will typically have a window 40.
  • This window 40 may attenuate low energy x-rays.
  • This window and/or the optical train may additionally comprise a filter, that such as a sheet or layer of aluminum, to further attenuate low energy x-rays.
  • the optical train comprises one or more x-ray optical elements in which the x-rays illuminate the inner surface of the element at a near-grazing angle (e.g. at angles of a few degrees or smaller), the critical angle will be exceeded for the higher energy x-rays, and they will not be reflected.
  • a near-grazing angle e.g. at angles of a few degrees or smaller
  • the critical angle will be exceeded for the higher energy x-rays, and they will not be reflected.
  • Such optics have a "high-energy cutoff' for reflection.
  • the "high-energy" cutoff is well defined for a given material and critical angle, and the attenuation of high energy x-rays prevents spurious signals coming from higher harmonics (e.g. twice (2x) the energy) from being observed downstream in the spectrometer.
  • higher harmonics e.g. twice (2x) the energy
  • additional structure in the reflectivity spectrum may be observed at high energy with some materials.
  • the reflectivity may be designed to be below 25% for all energies greater than 1.2 times the cutoff energy.
  • the reflectivity may be designed to be below 10% for all energies greater than 1.2 times the cutoff energy.
  • x-ray sources comprising targets of multiple "wires" of x-ray materials in close thermal contact with a thermally conductive substrate are used. This may be achieved by any number of methods known in the art, such as sputtering or by brazing multiple materials upon a substrate.
  • the electron beam and target may be moved relative to each other such that different target materials are bombarded and produce different spectra.
  • the x-ray generating materials are microstructured.
  • any of the target and/or source designs and configurations disclosed in the above referenced Patents and Patent Applications may be considered for use as a component in any or all of the methods or systems disclosed herein.
  • Such variations may include active cooling systems comprising channels that carry liquid near or into the target to remove heat.
  • the x-ray source used for various embodiments of the present technology may, as described, be a microfocus source using bombardment of a solid anode target by electrons or a target comprised of a metal layer deposited on a substrate.
  • the target may also comprise multiple x-ray generating materials, such as stripes of sputtered materials or wires brazed on a substrate, and/or may additionally contain regions in which the x-ray generating materials are molten or liquid.
  • the x-ray source may be any one of a number of other x-ray sources designed to use a liquid metal (such as a gallium liquid metal jet) as the anode.
  • the x-ray source target material(s) is preferably selected to optimize the generation of x-rays at energies slightly above the absorption edge of a predetermined element of interest.
  • FIGURE 2 An illustration of a portion of a target as may be used in some embodiments of the invention is presented in FIGURE 2 , in which an x-ray generating region comprising a single microstructure 700 is configured to be embedded into a substrate 1000 at or near a recessed edge 1003 of an optional recessed shelf 1002 near an edge of the substrate 1000.
  • the x-ray generating microstructure 700 can be in the shape of a rectangular bar of width W, length L, and depth or thickness D that is embedded in the substrate 1000 and generates x-rays 1488 when bombarded with electrons 111.
  • the thickness of the bar D (along the surface normal of the target) is selected to be between one third and two thirds of the electron penetration depth of the x-ray generating material at the incident electron energy.
  • the x-ray generating material used in the target should ideally have good thermal properties.
  • the x-ray generating material should additionally be selected for good x-ray production properties, which includes x-ray production efficiency (proportional to its atomic number) and in some cases, it may be desirable to produce a specific spectra of interest.
  • the material of the substrate 1000 may also be chosen to have a high thermal conductivity, typically larger than 100 W/(m °C) at room temperature.
  • the substrate may include one or high aspect ratio ("wire") microstructures.
  • FIGURE 3 illustrates a top view of a target having multiple wire microstructures.
  • Target 250 includes wire microstructures 320 and substrate 310. Spacing between the microstructures 320 may be lower bound to avoid creation of x-rays from an adjacent target when an electron-beam strikes a single target microstructure.
  • Microstructures 320 may be any of a plurality of metals or alloys, such as Ti, Al, Cu, Cr, Fe, Mo, Rh, Co, W, Pt, Ag, and Au, and each microstructure can be a different material from other microstructures, allowing each wire 320 to generate x-rays with different spectra. In some instances, multiple wires of the same material can be implemented in the present system, to provide a longer use or lifetime of the system.
  • Substrate 310 may be any highly thermal conductive material, such as for example diamond or copper.
  • the width of the space between microstructures Wc can be 15 ⁇ m (microns) or more.
  • the width of a wire microstructure Ws can be less than or equal to 250 or 300 ⁇ m (microns).
  • the substrate can extend longer than one or more microstructures, as shown in FIGURE 3 , or may have the same length and be flush with one or more microstructures.
  • the wire microstructures 320 can be embedded within the substrate 1000.
  • the embedded wires can have a cross section that is rectangular (as illustrated in FIGURE 32), curved, circular, square, or any other shape.
  • the target can have multiple surface mounted wire microstructures.
  • These may contain a material that prevents diffusion (e.g. Ta) and/or a material that improves the thermal conductance between the microstructures and substrate (e.g. Cr between Cu and diamond).
  • X-ray generating structures with at least one dimension smaller than 1 mm, or even as small as nano-scale dimensions (i.e. greater than 10 nm) may also be described by the word "microstructures" as used herein as long as the properties are consistent with the geometric factors for sub-source size and grating pitches set forth in the various embodiments.
  • Some microstructures may have one dimension (e.g. L) being several millimeters or in excess of 1 cm, with the other dimensions being sub-250 um for example.
  • the electron beam is directed onto different target materials either by moving the anode or by directing the electron beam by the use of electron control mechanism(s).
  • the x-ray source window is aligned such that the take-off angle of the x-rays are at fewer than 30 degrees.
  • FIGURE 4 An illustration of a portion of an alternative target as may be used in such embodiments of the present technology is presented in FIGURE 4 .
  • an x-ray generating region 710 with microstructures 711 - 717 is configured at or near a recessed edge 1003 of the target substrate 1000 on a shelf 1002 and generate x-rays 1788 when bombarded with electrons 111.
  • the bars may be embedded in the substrate (as shown) or on top of the substrate.
  • microstructures comprising multiple x-ray generating materials, microstructures comprising alloys of x-ray generating materials, microstructures deposited with an anti-diffusion layer or an adhesion layer, microstructures with a thermally conducting overcoat, microstructures with a thermally conducting and electrically conducting overcoat, microstructures buried within a substrate and the like.
  • FIGURES 5A - 5C illustrate an example of a target 1100-T comprising a set 710 of microstructures of x-ray generating material 711, 712... 717 embedded within a substrate 1000, similar to the target shown in FIGURE 4 .
  • the x-ray generating material When bombarded by electrons 111 within a vacuum chamber, the x-ray generating material produces x-rays 888.
  • a predetermined take-off direction (designated by ray 88-T) for the downstream formation of an x-ray beam.
  • This take-off direction is oriented at an angle ⁇ T relative to the local surface.
  • a predetermined set of cone angles is defined, centered around the take-off angle ⁇ T .
  • a ray propagating along the innermost portion of the cone makes an angle ⁇ 1 with respect to the take off angle, while a ray propagating along the outermost portion of the cone makes an angle ⁇ 2 with respect to the take off angle.
  • These cone angles are generally quite small (less than 50 mrad), and the take-off angle is generally between 0° to 6° (0 to 105 mrad), although in some circumstances a take off angle as large as 11.5° ( ⁇ 200 mrad) may be used.
  • FIGURE 6 represents a portion of a target having two sets of microstructures of x-ray generating materials as may be used in an alternative implementation.
  • one set of microstructures 710 comprises seven microstructures 711 - 717 of any material selected for the spectral x-ray radiation properties.
  • the target of FIGURE 6 also comprises a second set of microstructures 720, also comprising seven microstructures 721 - 727 of a second predetermined x-ray generating material, which is distinct from the first x-ray generating material.
  • a second set of x-rays 1888 are produced. As drawn, the x-rays 1888 emerge at a zero degree take-off angle relative to the surface but any non-zero take-off angle may be used. If the materials of the first set 710 and second set 720 are distinct, the corresponding x-rays 1788 and 1888 generated when selected for bombardment by electrons will also have distinct spectral properties.
  • multiple solid structures 740, 750 and 760 of different x-ray generating materials may be used in an anode target as well.
  • the physical translation of the target under the electron beam may allow the materials to be "switched" from one to another while producing a beam that remains aligned with a single set of x-ray optics
  • other embodiments in which the electron beam is simply directed from one set of materials to another may also be used. This may be beneficial in cases where the different x-ray generating materials are aligned with different sets of x-ray optics, with each set of optics tuned to match the radiation spectrum of x-rays for each material.
  • a target material and optical system may be considered "matched" when the cutoff energy of the optical system is above a strong characteristic line of the target material and when the optical system is designed to optimize reflection of the selected characteristic line.
  • this optical system will comprise x-ray reflectors that collect and focus x-ray energies of a bandwidth greater than 0.1% of an x-ray energy of interest.
  • the generated x-rays will diverge from the x-ray source 80, and an optical train 3000 comprising a set of one or more x-ray optical elements will collect a portion of the x-rays and redirect their path of propagation.
  • the optical train 3000 may be a simple, single x-ray reflecting optical element with the topology of a hollow tube (e.g. capillary tube), or a more complex set of x-ray optics.
  • This optical train 3000 can be aligned along the axis of brightest illumination so that a portion of the diverging x-rays 888 will reflect off the inner surface.
  • the curvature of the inner surface may take a number of geometric forms, but a very useful set of geometric forms for a number of optical elements are found among the quadric surfaces. Examples of reflecting surface profiles corresponding to one or more portions of ellipsoids, paraboloids, hyperboloids, elliptic cylinders, cylinders, and conical (or 2D versions of the 3D shapes mentioned above).
  • the optical train produces a focused beam of x-rays.
  • an optional aperture 272 may be placed in the same plane as the focal plane to reduce background from scattered x-rays which helps to improve the signal-to-background ratio of the system.
  • FIGURE 8A illustrates in cross section a possible optical configuration for the optical train using the form of an ellipse.
  • An elliptical capillary optic has two foci F 1 and F 2 such that any photons radiating from one of the foci will be reflected and converge onto the other.
  • FIGURES 8A -8B illustrate a portion of an embodiment of the invention utilizing such an ellipsoidal reflector 3010.
  • An x-ray source generates diverging x-rays 888 that enter the ellipsoidal optical element 3010. A portion of the x-rays experience total external reflection from the inner elliptical surface of a tube-like optical element 3010, and become focused x-rays 887 that pass through an object 250 to be examined and arrive at a focal point.
  • An aperture 272 in aperture component 270 is placed coincident with the focal plane.
  • FIGURE 8A illustrates x-rays 888 generated by bombarding microstructures 1700 with electron beam 111.
  • x-rays 888 are illustrated as emitting from a single point on microstructure 1700, the x-rays may be generated by different and/or all portions of a microstructure.
  • the emission of x-rays from a single point in FIGURE 8A and other figures is illustrated for purposes of simplicity and not intended to be limiting.
  • the on-axis x-rays may be blocked with a beam stop 1850.
  • beam stop 1850 of the system of FIGURE 8A and in other systems and configurations disclosed herein, may be positioned on the incident beam side of the optical element 3010 or other locations (e.g. exit).
  • the optic element of the system described herein may include one or more reflectors that are matched to one or more target materials.
  • the matching may be achieved by selecting optics with the geometric shape, size, and surface coating that collects as many x-rays as possible from the source and at an angle that satisfies the critical reflection angle of the x-ray energies of interest from the target.
  • the matching is based on maximizing the numerical aperture (NA) of the optics for x-ray energies of interest.
  • NA numerical aperture
  • the optic elements may be configured to focus or collimate the beam.
  • a possible optical configuration for the optical train uses the form of two parabolas.
  • a parabola can have a single focus F p such that any photons radiated from the point of focus will be reflected to form a parallel (collimated) beam.
  • FIGURE 9A-9B illustrates a portion of an embodiment of the invention utilizing a paraboloidal reflector 3020.
  • Electron beams 111 bombard a target 1000, which is at a near zero angle (as shown), to provide an x-ray source or at a shallow angle such as 6 degrees.
  • the x-ray source generates diverging x-rays 888 that enter a first paraboloidal optical element 3020.
  • a portion of the x-rays experience total external reflection from the inner paraboloidal surface of the tube-like optical element 3020, and become collimated x-rays 889.
  • a second optical element 3022 with a tube-shaped topology and paraboloidal inner surface may be aligned with the optical axis of the first optical element 3020 so that the collimated x-rays 889 are incident on the inner surface of the second optical element 3022 at angles smaller than the critical angle for the surface.
  • this second optical element is not a separate component but instead a different profile prescription than the first optical element and contained within the same capillary.
  • the reflected x-rays then become focused x-rays 887 that converge onto a focal point after passing through an object 240 to be examined.
  • An optional aperture 272 is placed at the focal plane of the second optical element.
  • the illustration shows a second paraboloidal optical element 3022 of the same size and shape as the initial paraboloidal optical element 3020, these need not be the same dimensions and may have different curvature and relative focus positions.
  • the on-axis x-rays may be blocked with a beam stop 1852.
  • the beam stop may be positioned at different positions with respect to the optic, including at the entrance to the first optical element 3020 or at the exit of the second optical element 3022 as well.
  • x-ray optical systems such as Wolter Type I optics, cone shaped capillary optics, polycapillary optics, Kirkpatrick-Baez optics, Montel mirrors, etc. may be used as components of the optical train. Systems comprising filters and additional beam stops, etc. may also be used.
  • optical elements described above may be fabricated of any number of optical materials, including glass, silica, quartz, BK7, silicon (Si), Ultra-low expansion glass (ULE TM ), Zerodur TM or other elemental materials.
  • the reflective coatings used for the various optical elements used in embodiments of the invention as described above may be a single elemental material, to take advantage of the total external reflection for angles of incidence smaller than the critical angle, and preferably may be coated with a layer of higher mass density material (greater than 2.5 g/cm 3 ) at least 25 nm thick. Materials such as gold (Au), silver (Ag), platinum (Pt), etc. may be used as single-material coatings for these optical elements.
  • the reflective coatings may also be multilayer coatings, with alternating periodic layers of two or more materials, that provide constructive interference in reflection for certain x-ray wavelengths.
  • the reflection efficiency depends on the wavelength and angle of incidence of the x-rays as well as the thickness of the alternating layers, so this has limited use as a broad band reflector, but may be used if a narrow energy band is desired.
  • Combinations that may be used for multilayer reflectors are tungsten/carbon (W/C), tungsten/silicon (W/Si), tungsten/tungsten silicide (W/WSi 2 ), molybdenum/silicon (Mo/Si), nickel/carbon (Ni/C), chromium/scandium (Cr/Sc), lanthanum /boron carbide (La/B 4 C), tungsten/boron carbide (W/B 4 C), and tantalum/silicon (Ta/Si), among others.
  • the surface may also be a compound coating comprising an alloy or mixture of several materials.
  • x-ray optical elements such as Fresnel Zone Plates, cylindrical Wolter optics, Wolter Type II or III optics, Schwarzschild optics, diffraction gratings, crystal mirrors using Bragg diffraction, hole-array lenses, multi-prism or "alligator” lenses, rolled x-ray prism lenses, "lobster eye” optics, micro channel plate optics may be used or combined with those already described to form compound optical systems for embodiments of the invention that direct x-rays in specific ways that will be known to those skilled in the art.
  • x-ray optical elements such as Fresnel Zone Plates, cylindrical Wolter optics, Wolter Type II or III optics, Schwarzschild optics, diffraction gratings, crystal mirrors using Bragg diffraction, hole-array lenses, multi-prism or "alligator” lenses, rolled x-ray prism lenses, "lobster eye” optics, micro channel plate optics may be used or combined with those already described
  • FIGURES 10-12 illustrate schematic cross-section views and a perspective view the elements of a spectrometer system that may be used in some embodiments of the invention.
  • the x-ray target 1100 comprising a substrate 1000 and x-ray generating material 1700 is bombarded by electrons 111 in a vacuum.
  • the x-rays 888 emerge at a non-zero take-off angle relative to the surface.
  • the x-rays 888 that diverge from the x-ray source pass through the window 40 in the vacuum chamber and are collected by an optical train.
  • the optical train comprises a single capillary optic 3010 and a beam stop 1854.
  • This single optic 3010 has an inner ellipsoidal surface that reflects x-rays at near-grazing angles and focuses them onto a focal point.
  • An optional aperture 272 with an aperture component 270 is coincident at the focal point.
  • An object 240 to be examined is positioned before the aperture component 270, and the x-rays passing through the aperture 272 are those that have been transmitted through the object 240.
  • the aperture 272 will typically be a small hole of a diameter comparable to the size of the focused spot produced by the x-ray optical train. Aperture diameters of 5 to 25 microns may be typical in some embodiments of the invention.
  • the aperture may comprise a slit, generally oriented horizontally (i.e. in the direction parallel to the sagittal plane).
  • the aperture component itself may comprise a piece of metal (e.g. molybdenum or platinum) having a thickness shorter than the depth of focus for the optical system (e.g. on the order of 20 microns thick).
  • the x-rays emerge from the point of focus as diverging x-rays 888-T.
  • the geometry will generally be an annulus of x-rays, as defined by the focusing lens 3010.
  • the aperture 272 serves as the point of origin for the x-rays entering the spectrometer 3700. Additional apertures may also be used within the spectrometer, such as in front of the detector.
  • the spectrometer is a parallel detection spectrometer as known in the art [see “DB Wittry, 'X-ray crystal spectrometers and monochromators in microanalysis.' Microsc. Microanal. 7, 124-141 2001 "].
  • the diverging annular cone of x-rays 888-T will fall onto the surface of a diffracting analyzer crystal 3710, which will diffract x-rays of different wavelengths ⁇ 1 , ⁇ 2 , ⁇ 3 ⁇ 4 , etc.
  • the crystal analyzer will act as a Bragg diffraction element. X-rays that are not diffracted 899 are typically transmitted through the crystal analyzer and may be absorbed by a beam stop (not shown).
  • the crystal analyzer 3700 may be positioned -250 mm away from the aperture 272 and will typically have a width of about 2 cm. and a length of about 5 cm, but other dimensions may be used.
  • the crystal analyzer 3700 may comprise a single planar Bragg crystal, but in practice, the analyzer crystal may also comprise a thin crystal curved in the sagittal direction. This allows the x-rays diverging in the directions perpendicular to the direction of propagation to be collected and focused onto the detector 290, while allowing the x-rays to be diffracted by wavelength along the direction of propagation. Such orientations are sometimes called a von Hamos Spectrometer. In some implementations, the crystal may be doubly curved.
  • a bending radius between 50 and 200 mm may be used.
  • parallel detection spectrometers may be of geometries and designs that have been proposed by Schnopper, Birks, Henke, Zaluzec, Fiori, and others.
  • Curved crystal analyzers such as those made from thin wafers of single crystal silicon (e.g. aligned with the surface along the 111 or the 220 planes) may be used in some embodiments of the invention.
  • Single crystal silicon analyzers may be grown onto a curved substrate, or thinned from previously grown silicon wafers and bent.
  • Crystal analyzers comprising graphite may also be used, in particular those comprising graphite layers aligned along the 002 plane such as highly oriented pyrolytic graphite (HOPG), or highly annealed pyrolytic graphite (HAPG).
  • the crystals may include HOPG(002) and HAPG(002).
  • a graphite layer between 15 and 200 microns thick is grown onto a curved substrate.
  • Dispersion is achieved because the diverging cone has a variety of angles of incidence on the crystal analyzer, and therefore for at least some angle of incidence, x-rays of a particular energy within the designated x-ray bandwidth may be reflected. However, all other wavelengths at the same angle of incidence will not be diffracted, and will simply pass through the crystal analyzer shown as transmitted x-rays 899 in FIGURES 11 and 12 .
  • FIGURE 12 illustrates a geometry of the spectrometer used in some embodiments.
  • Spectrometer 3730 uses a crystal analyzer in the form of a mosaic crystal 3733.
  • the crystal analyzer comprises an ensemble of micro-crystals at varied angles throughout the material, each as small as a few hundred nanometers or as large as several microns, held with a backing 3734, typically made of metal.
  • the mosaic crystal can be curved at least in the sagittal non-dispersive direction. Transmitted x-rays that were not diffracted by the micro-crystal at the surface may still be diffracted from another micro-crystal positioned deeper within the mosaic.
  • the origin of x-rays (the focal point of the x-ray optics), the diffracting crystal, and the point of convergence at the detector all fall along the Rowland Circles 808-A and 808-D for the corresponding wavelengths.
  • other micro-crystals are present in the mosaic crystal, only those that lie along the Rowland Circle and have the correct orientation will diffract x-rays to converge to the same position at the detector 290.
  • X-rays of varying wavelengths distributed throughout the diverging beam 888-T have a better chance of encountering a properly positioned and oriented micro-crystal.
  • Use of mosaic crystals can collect as much as 100 times the amount of x-rays that a single crystal diffraction element can produce. Note that although micro-crystals with "random" orientations are illustrated to dramatically illustrate the mosaic non-uniformity, most mosaic crystals will be more aligned.
  • FIGURE 13A illustrates a spectrometer design based on a Rowland Circle geometry with a crystal that is curved to Johansson geometry.
  • the crystal could be curved to Johann geometry.
  • the crystals could be singly curved -- that is, curved only in the dispersion plane and flat in the sagittal (or vertical) plane.
  • the crystals could be doubly curved -- that is, curved in both dispersion and sagittal planes. Examples of such doubly curved crystals include, but not limited to, spherical Johann, Toroidal Johann, Spherical Johansson and Wittry crystals.
  • an apparent source 272 behind the sample 1000 emits x-rays toward the Johansson crystal 3710.
  • the apparent source is often produced by an apertured or focused x-ray beam generated from a laboratory x-ray source in combination with an optic as has been previously described, or in some instances, by electron bombardment of a sample in an electron microscope.
  • the focal spot of the focused x-ray beam is coincident with a sample - in other instances, the focal spot is behind the sample 1000 and is coincident with an aperture (not shown).
  • the x-rays are transmitted through the sample and propagate towards Johansson crystal 3710, which focuses the x-rays to a spatially resolving detector 293.
  • the placement of the apparent source 272 within the Rowland circle is known as an off-Rowland circle geometry.
  • a sample 1000 can be placed on the Rowland circle.
  • the source 80 can be located further away from the Rowland circle and direct x-rays to the sample 1000, with an optional x-ray optic placed between the x-ray source 80 and the sample 1000.
  • the sample 1000 may furthermore be placed slightly before the focal point of a focusing optical system if it is employed.
  • the sample acts as an apparent source of x-rays and crystal 3710 disperses the x-rays.
  • the x-ray detector 293 simultaneously detects all the x-rays dispersed by the crystal 3710 over a certain angular range.
  • the implementations illustrated in FIGURES 13A and 13B are sometimes referred to as parallel detection.
  • an apparent source 272 is located on the Rowland circle and directs x-rays 888 to a Johann crystal 3710, which collects the x-rays and focuses x-rays 887 on the sample 1000 that is located on the Rowland circle.
  • An x-ray detector 293 is behind the sample to collect all x-rays transmitted through the sample.
  • the x-ray detector 293 could be a point detector such as, but not limited to, Silicon Drift Detector, Gaseous Proportional counter, solid state detectors etc.
  • detection efficiency is optimized for only a single x-ray wavelength (or extremely narrow bandwidth of x-rays) rather than multiple wavelengths as in the case of parallel detection x-ray spectrometers.
  • the relative alignment of the x-ray origin, crystal, and detector, as well as parameters of the Rowland Circle (e.g. diameter), can be changed by motion of one or more of the components.
  • XANES x-ray absorption near edge spectroscopy
  • EXAFS extended x-ray absorption fine structure
  • the sample may be a thin film or structure existing on a substrate that may be too thick for the x-rays of energies of interest to transmit through the sample.
  • reflection geometry may be preferred.
  • the x-rays are typically incident on the sample at a very shallow incident angle, typically below a couple of degrees to meet the condition of total reflection at the film/substrate and/or structure/substrate interface.
  • the x-rays penetrate through the film or structure of interest but get reflected at the interface of the film/substrate or structure/substrate interface and emerge from the same side of the sample as the incident beam. This avoids the problem of insufficient transmission of x-rays through the sample.
  • this geometry may be used for XANES and EXAFS.
  • the spectrometer may use different crystal types for different regimes of the x-ray absorption spectroscopy acquisition.
  • the spectrometer uses at least two different crystal types: with at least one being a single crystal and at least one being a mosaic crystal.
  • the single crystal may be a flat crystal that is aligned to measure the x-ray wavelength of interest.
  • the crystal is curved in a tangential direction (e.g. Johann, Johannsson).
  • the single crystal and an x-ray detector are used for the acquisition of XANES information.
  • An apparent source of x-rays, crystal, and detector are aligned such that the apparent source is either on or within a Rowland circle.
  • the apparent sample spot is achieved by either an aperture or through direct focused illumination on the sample using an x-ray optical train.
  • the Rowland circle is a circular geometry in which an apparent source of x-rays on the sample, the crystal, and a detector can be placed so that the spectral lines are to be brought into focus on the detector.
  • the apparent source of x-rays is placed within the Rowland circle, multiple x-ray energies can be dispersed along the detector and an x-ray detector with energy dispersive capabilities can be used. In some embodiments, this may be a CCD detector with sufficiently fast readout speeds. In other embodiments, this may be an energy dispersive array detector. In some embodiments, if the apparent source of x-rays is placed on the Rowland circle, a narrow range of wavelengths is received by the detector.
  • the crystal may be used for serial detection by placing the single crystal on a Rowland circle.
  • the single crystal may be used for parallel detection by placing the apparent source of x-rays within a Rowland circle (off-Rowland geometry).
  • the XANES spectrum is obtained, it can be then normalized by the direct beam spectrum acquired by removing the sample from the beam.
  • Single crystals used may include Si(111), Si(220), Si(400), Ge(111), Ge(220), Ge(400), and Ge(620).
  • the mosaic crystal and at least one spatially resolving x-ray detector (referred to as a "mosaic crystal spectrometer") is used for the acquisition of EXAFS information.
  • the mosaic crystal is a curved in the sagittal direction and the apparent source, mosaic crystal, and detector are aligned in a parallel detector geometry.
  • the system may then be used with a different set of crystals, such as HOPG crystals, to focus x-rays at a spatially resolving detector in a parallel detection geometry such as von Hamos for acquisition of EXAFS spectrum.
  • the different set of crystals can be positioned in a position suitable for focusing x-rays at the spatially resolving detector.
  • the crystals may be interchangeable and positioned using electro-mechanical mechanisms, or may be stationary as a source is positioned to provide x-rays at the currently selected crystal.
  • normalization can be performed by acquiring the direct beam spectrum by removing the sample from the beam.
  • the XANES and EXAFS data can be processed by a spectra processing mechanism, which can be implemented for example by signal processing electronics 292 an analysis system 295.
  • a spectra processing mechanism which can be implemented for example by signal processing electronics 292 an analysis system 295.
  • the near edge portion of the EXAFS spectrum can be replaced with the XANES spectrum resulting in the XANES and EXAFS spectra combined together in a unique fashion to provide a complete XAS spectrum with no loss in information.
  • This unique method provides for a complete and a more refined XAS analysis.
  • two spectrometer designs or a single spectrometer capable of being used in the above approach are two spectrometer designs or a single spectrometer capable of being used in the above approach.
  • FIG 13D illustrates a schematic perspective view of a system using a curved crystal analyzer that distributes the spectrum along one axis, while focusing x-rays in the other (sagittal) axis.
  • the detector may be any x-ray counting detector.
  • the spatially resolving detector 290 may comprise a 2D or 1D array sensor 294. In some embodiments of 2D arrays, one axis may be significantly longer than the other. A 2048 x 256 pixel array may be used, although a detector with at least 128 pixels along the long axis (the dispersive direction) may be preferred. In such embodiments, it is preferred that the long axis will be aligned along the direction of x-ray propagation, and the dispersion of x-rays by wavelength will occur along that axis. The short axis will be aligned with the sagittal direction.
  • a 1-D array detector 1 pixel wide may be used, but as a practical matter, the diffracted x-rays may not form a perfect spot, and so detection using multiple pixels may provide a higher collection efficiency.
  • the spatially resolving detector 290 may be any one of a number of x-ray array detectors, such as a CCD array (x-ray sensor), a CMOS or S-CMOS detector, a flat panel sensor, or any one or more position sensitive x-ray array detectors known in the art that converts x-ray intensity to an electronic signal, including 1-D line and 2-D array detectors.
  • position-sensitive detectors include linear detectors, position-sensitive array detectors, pin diodes, proportional counters, spectrometers, photodiode detectors, scintillator-type and gas-filled array detectors, etc.
  • the detector may include one or more detector elements of any type that detects x-rays, including proportional and avalanche detectors or energy-dispersive elements.
  • detector variations may also be used in other embodiments of the invention.
  • additional spectral filters may be used between the object and the detector to select a certain portion of the x-rays emerging from the object for detection. This may be especially useful if there is a significant amount of x-ray fluorescence from the object that may interfere with the signals generated by the transmitted x-rays.
  • a second detector may be included to detect the intensity of the incident x-rays, allowing normalization of the transmitted signal with any variations in the incident x-ray intensity.
  • Energy resolving pixel array detectors may also be used. In these detectors, each pixel also provides information on the energy of x-rays detected, and may be especially useful when the object produces significant fluorescence.
  • the silicon PIN photodiode (Si-PIN) is a simple and low cost class of EDS spectrometer that typically has the lowest performance in terms of energy resolution.
  • Energy resolving pixel array spectrometers are available and may be used in some embodiments of the invention.
  • Another type of detector is known as a pixel array microcalorimeter spectrometer. In some instances, a CCD detector with a sufficiently fast readout speed serves as an energy resolving detector.
  • Additional configurations may involve additional filters (e.g. thin foils containing the appropriate element(s)) along the beam path before the detector to preferentially attenuate some unwanted x-rays from arriving at the spectrometer, reducing the background due to the detection of the x-rays scattered from the object or reduce total x-ray flux entering by the spectrometer to avoid saturation.
  • additional filters e.g. thin foils containing the appropriate element(s)
  • Multiple spectrometers of the same type or combination of two or more types can be used simultaneously or interchangeable to utilize their respective strength individually or collectively.
  • an aperture or slit component may be placed before the detector.
  • Other detector geometries and arrangements for x-ray fluorescence may be known to those skilled in the art. For more on x-ray detectors, see Albert C. Thompson, "X-Ray Detectors", Section 4.5 of the X-ray Data Booklet, which may be downloaded at: xdb.lbl.gov/Section4/Sec_4-5.pdf.
  • FIGURE 14 provides a schematic illustration of a spectrometer system having a diversity of options built into the system.
  • the target 1102 comprises a substrate 1002 and two (or more) different types of x-ray generating materials 1702 and 1704.
  • the mount 34 upon which the target is secured not only connects to the electrical lead 32, but also has a controller 36 that allows physical motion in a lateral direction for the selection of the material to be bombarded by electrons 111.
  • the system of FIGURE 14 also has multiple different optical trains 3010-A, 3010-B and 3010-C supported in a mount 3016 that allows the set of optical trains to be moved laterally to allow alignment of any of the optical trains (which may use different material coatings and filters inside to allow different x-ray bandwidths) with any of the x-ray generating targets 1702, 1704 etc.
  • the rightmost x-ray generating material 1704 is being bombarded by electrons, and the left most optical train 3010-A is positioned to collect the x-rays transmitted through the window 40.
  • the mount that provides for movement of the x-ray optical systems allows for selecting which x-ray optical system will collect x-rays from the x-ray source.
  • the converging x-rays 887 emerging from the optical train are focused onto an aperture 272 in an aperture component 270, and also pass through the object 240 to be investigated.
  • the resulting x-rays diverging from the aperture 272 become the apparent source of the x-rays diffracted by the spectrometer 3700.
  • the aperture component 270 may have multiple openings, such as circular apertures 272 and 274 having different sizes, or slits 275 and 277 of different sizes.
  • the spectrometer 3731 comprises a mosaic analyzer crystal 3733 that disperses the x-rays onto the x-ray sensor 294 of the detector 290.
  • this spectrometer 3731 also comprises a mount 3740 that allows the analyzer crystal 3710 to rotate about an axis perpendicular to the direction of x-ray propagation. This allows a larger range of x-ray dispersion to be measured using a single detector.
  • Such a multi-source / multi optic system may be used to collect x-ray spectra in a sequence of bands (e.g. combinations for different 1 keV bands). Rotation of the crystal about the axis may expand the range of energies collected by from the same source/optic combination.
  • optical trains with a variety of beam stops may be used.
  • Beam stops may be positioned at the entrance to the optical train, at the exit of the optical elements of the optical train, or in between elements of the optical train.
  • a number of shielding elements may be used to block or reduce unwanted x-rays from being detected.
  • an x-ray fluorescence detector is used to monitor incident x-rays and/or monitor the elemental composition of the sample.
  • the entire system (and not just the x-ray source) may be enclosed in a vacuum chamber, removing the need for the window 40 be present to maintain the vacuum around the x-ray source.
  • the optical train and spectrometer may be flushed with helium gas, to reduce scattering in the system.
  • the sample is moved relative to the spectrometer to perform 2D mapping or 3D tomography of XAS information.
  • FIGURE 15 illustrates a method for efficiently obtaining x-ray absorption spectroscopy information using multiple crystals.
  • An element of interest is selected within a predetermined sample at step 1510.
  • the element may be selected by an x-ray absorption spectrometer (XAS) system in response to receiving input from a user.
  • XAS x-ray absorption spectrometer
  • An absorption edge x-ray energy of interest may then be identified at step 1520.
  • the absorption edge can be identified by the present system in response to user input received by the present system.
  • the sample can be illuminated using an x-ray beam having an x-ray bandwidth inclusive of the absorption edge energy at step 1530.
  • the x-ray beam can be provided by micro-focus x-ray source or other source.
  • the absorption edge may be for an element of interest within the predetermined sample.
  • a first absorption spectrum is acquired using a single crystal spectrometer as XANES data at step 1540.
  • the absorption spectrum can be acquired at high spectral resolution of greater than, for example, 3 eV, for a bandwidth of x-ray energies near and inclusive of the selected absorption edge.
  • a second absorption spectrum is acquired using a mosaic crystal spectrometer as EXAFS data at step 1550.
  • the EXAFS data can have a coarser spectral resolution than the XANES data absorption spectrum acquired using the single crystal spectrometer.
  • the second spectrum is acquired for a bandwidth of x-ray energies wider than the bandwidth of x-rays acquired by the single crystal spectrometer.
  • the absorption spectrum can be inclusive of the absorption edge such that the absorption spectrum data acquired using the mosaic crystal spectrometer contains at least the extended x-ray absorption fine structure (EXAFS) data.
  • the acquired XANES spectra data and EXAFS spectra data can be processed to produce x-ray absorption spectroscopy data at step 1560.
  • the produced x-ray absorption spectroscopy data nearest to the absorption edge is refined with the higher spectral resolution spectrum obtained by the single crystal spectrometer.
  • only one absorption spectrum will be acquired by either a single crystal spectrometer as XANES or a mosaic crystal spectrometer as EXAFS.
  • the results will be compared to a library of standards as a "fingerprint" for refining the analysis.

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pathology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Claims (15)

  1. Procédé de réalisation d'une spectroscopie d'absorption des rayons X, le procédé comprenant les étapes consistant à :
    éclairer un objet à l'aide d'un faisceau de rayons X dont la bande passante énergétique est supérieure à 0,1 % et incluant l'énergie correspondant à un bord d'absorption d'un élément atomique ;
    acquérir un premier spectre d'absorption des rayons X de l'objet à une première résolution énergétique meilleure que 3 eV, à l'aide d'un spectromètre à monocristal, sur une première bande passante énergétique incluant le bord d'absorption ;
    acquérir un deuxième spectre d'absorption des rayons X de l'objet à l'aide d'un spectromètre à cristal mosaïque à une deuxième résolution en énergie plus grossière que la première résolution en énergie et sur une deuxième bande passante énergétique plus large que la première bande passante énergétique et incluant ledit bord d'absorption ; et
    traiter le premier et le deuxième spectre d'absorption des rayons X pour produire un troisième spectre d'absorption des rayons X dans lequel le deuxième spectre d'absorption des rayons X dans la première bande passante énergétique correspondant au premier spectre d'absorption des rayons X est affiné à l'aide du premier spectre d'absorption des rayons X.
  2. Procédé selon la revendication 1, comprenant en outre la focalisation du faisceau de rayons X sur l'objet à l'aide d'au moins une optique capillaire réfléchissante de focalisation des rayons X, la bande passante énergétique incluant ledit bord d'absorption et ayant des énergies supérieures à 100 eV au-dessus du bord d'absorption.
  3. Procédé selon la revendication 1, dans lequel le spectromètre à monocristal comprend un monocristal incurvé au moins dans le plan de dispersion, dans lequel facultativement l'acquisition du premier spectre d'absorption des rayons X comprend l'utilisation d'un détecteur à résolution spatiale pour détecter des rayons X dispersés par le monocristal alors que l'objet, le monocristal et le détecteur à résolution spatiale sont dans une géométrie hors du cercle de Rowland.
  4. Procédé selon la revendication 1, comprenant en outre les étapes consistant à :
    sélectionner l'élément atomique à l'intérieur ; et
    identifier une énergie des rayons X de bord d'absorption dudit élément atomique pour effectuer une mesure par spectroscopie d'absorption des rayons X.
  5. Procédé selon la revendication 1, dans lequel le spectromètre à cristal mosaïque comprend un cristal mosaïque incurvé au moins dans la direction sagittale de dispersion, et l'acquisition du deuxième spectre d'absorption des rayons X comprend l'utilisation d'un détecteur de rayons X à résolution spatiale pour détecter des rayons X dispersés par le cristal mosaïque alors que le cristal mosaïque et le détecteur à résolution spatiale sont dans une géométrie de Von Hamos.
  6. Procédé selon la revendication 1, dans lequel :
    le premier spectre d'absorption des rayons X contient au moins une partie d'un spectre d'absorption des rayons X à structure de bord proche (XANES) ; et/ou
    le deuxième spectre d'absorption des rayons X contient au moins des données de structure fine d'absorption des rayons X étendue (EXAFS).
  7. Système de spectroscopie d'absorption des rayons X, le système comprenant :
    une source de rayons X (80) ;
    une fixation (244) configurée pour supporter un objet (240) à examiner ;
    au moins une optique de focalisation des rayons X (3000) configurée pour collecter les rayons X de ladite source de rayons X avec une bande passante énergétique supérieure à 0,1 % d'une énergie de rayons X correspondant à un bord d'absorption d'un élément atomique à détecter dans l'objet, la bande passante énergétique incluant l'énergie de rayons X correspondant au bord d'absorption, l'au moins une optique de focalisation des rayons X étant en outre configurée pour focaliser une partie des rayons X collectés sur une tache focale avec une taille de focalisation inférieure à 500 micromètres ;
    au moins un spectromètre (3700) comprenant :
    au moins un monocristal (3710) incurvé au moins dans la direction de dispersion et ayant une première résolution énergétique meilleure que 3 eV sur une première bande passante énergétique incluant le bord d'absorption ;
    au moins un cristal mosaïque (3733) ayant une deuxième résolution énergétique plus grossière que la première résolution énergétique sur une deuxième bande passante énergétique plus large que la première bande passante énergétique ; et
    au moins un détecteur de rayons X à résolution spatiale (290) configuré pour détecter les rayons X transmis à travers l'objet.
  8. Système selon la revendication 7, dans lequel une surface réfléchissante de l'au moins une optique de focalisation des rayons X comprend des revêtements multicouches.
  9. Système selon la revendication 7, comprenant en outre :
    un moyen de positionner le point focal, l'au moins un monocristal, et l'au moins un détecteur de rayons X à résolution spatiale dans une géométrie hors du cercle de Rowland pour une détection parallèle ;
    un moyen de positionner le point focal, l'au moins un cristal mosaïque et l'au moins un détecteur de rayons X à résolution spatiale dans une géométrie de Von Hamos ; et
    un système de traitement configuré pour normaliser et aligner un spectre d'absorption des rayons X monocristallin obtenu avec l'au moins un monocristal et un spectre d'absorption des rayons X de cristal-mosaïque obtenus avec l'au moins un cristal mosaïque pour produire un spectre d'absorption des rayons X combiné dans lequel le spectre d'absorption des rayons X de cristal-mosaïque dans une bande passante énergétique correspondant au spectre d'absorption des rayons X monocristallin est affiné à l'aide du spectre d'absorption des rayons X monocristallin.
  10. Système selon la revendication 9, dans lequel
    le spectre d'absorption des rayons X monocristallin a une résolution en énergie meilleure que 3 eV sur une bande passante énergétique de 10 eV à 100 eV ; ou
    le spectre d'absorption des rayons X de cristal-mosaïque a une résolution en énergie plus grossière que 3 eV sur une bande passante énergétique de plus de 100 eV.
  11. Système selon la revendication 7, dans lequel l'au moins une optique de focalisation des rayons X comprend une optique capillaire à rayons X ayant une surface réfléchissante intérieure, dans lequel au moins une partie de la surface réfléchissante intérieure est une partie d'une surface quadrique, facultativement dans lequel la partie de la surface réfléchissante intérieure est recouverte d'un matériau dont le numéro atomique est supérieur à 26 et qui est axialement symétrique.
  12. Système selon la revendication 11, comprenant en outre une ouverture configurée pour laisser passer sélectivement les rayons X transmis à travers l'objet tout en ne laissant pas passer les rayons X de fluorescence provenant de l'objet, dans lequel l'ouverture étant facultativement placée au point focal de l'optique de focalisation des rayons X ou à proximité de celui-ci.
  13. Système selon la revendication 7 ou selon la revendication 9, dans lequel la source de rayons X comprend une pluralité de matériaux cibles de rayons X et un générateur de faisceau d'électrons configuré pour générer un faisceau d'électrons et pour bombarder un matériau cible de rayons X sélectionné parmi la pluralité de matériaux cibles de rayons X avec le faisceau d'électrons, dans lequel la source de rayons X comprend en outre facultativement un mécanisme pour modifier la position relative de la pluralité de matériaux cibles de rayons X et du faisceau d'électrons.
  14. Système selon la revendication 9, dans lequel le moyen de positionner le point focal, l'au moins un monocristal et l'au moins un détecteur de rayons X à résolution spatiale dans une géométrie hors du cercle de Rowland comprend en outre un moyen de modifier une distance entre le point focal et l'au moins un monocristal pour sélectionner la bande passante énergétique du spectre d'absorption des rayons X monocristallin.
  15. Système selon l'une quelconque des revendications 7 à 14, dans lequel l'au moins un monocristal comprend un cristal de Johansson.
EP18771876.2A 2017-03-22 2018-03-21 Procédé de réalisation d'une spectroscopie des rayons x et système de spectromètre d'absorption de rayons x Active EP3602020B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762475213P 2017-03-22 2017-03-22
PCT/US2018/023547 WO2018175570A1 (fr) 2017-03-22 2018-03-21 Procédé de réalisation d'une spectroscopie des rayons x et système de spectromètre d'absorption de rayons x

Publications (3)

Publication Number Publication Date
EP3602020A1 EP3602020A1 (fr) 2020-02-05
EP3602020A4 EP3602020A4 (fr) 2021-07-28
EP3602020B1 true EP3602020B1 (fr) 2023-12-27

Family

ID=68921944

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18771876.2A Active EP3602020B1 (fr) 2017-03-22 2018-03-21 Procédé de réalisation d'une spectroscopie des rayons x et système de spectromètre d'absorption de rayons x

Country Status (2)

Country Link
EP (1) EP3602020B1 (fr)
CN (1) CN110621986B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112563092B (zh) * 2020-12-08 2022-09-23 佛山宁宇科技股份有限公司 单晶化抗蒸发的x射线球管阳极靶的制造工艺
CN113345619B (zh) * 2021-06-16 2022-07-12 中国工程物理研究院激光聚变研究中心 一维x射线折射闪耀波带片
CN114486971A (zh) * 2022-01-25 2022-05-13 深圳市埃芯半导体科技有限公司 多源设计的x射线分析系统和方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001188052A (ja) * 1999-12-28 2001-07-10 Rigaku Corp Ｘａｆｓ測定装置
CN1829910B (zh) * 2003-06-02 2012-05-23 X射线光学系统公司 实现xanes分析的方法和设备
JP5320807B2 (ja) * 2008-04-25 2013-10-23 株式会社島津製作所 波長分散型ｘ線分光器
JP2010032341A (ja) * 2008-07-29 2010-02-12 Photon Production Laboratory Ltd Ｘ線分析装置
JP2012130586A (ja) * 2010-12-22 2012-07-12 Fujifilm Corp 放射線画像検出装置、放射線撮影装置、及び放射線撮影システム
CN102507623B (zh) * 2011-10-14 2014-03-05 深圳市世纪天源环保技术有限公司 一种非扫描式波长色散型x射线荧光光谱仪
US20150092924A1 (en) * 2013-09-04 2015-04-02 Wenbing Yun Structured targets for x-ray generation
US9449781B2 (en) * 2013-12-05 2016-09-20 Sigray, Inc. X-ray illuminators with high flux and high flux density
US9448190B2 (en) * 2014-06-06 2016-09-20 Sigray, Inc. High brightness X-ray absorption spectroscopy system
CN103604818B (zh) * 2013-11-21 2016-11-09 同济大学 一种荧光exafs数据的自吸收效应修正处理方法
WO2015187219A1 (fr) * 2014-06-06 2015-12-10 Sigray, Inc. Système de mesure d'absorption des rayons x
US10295486B2 (en) * 2015-08-18 2019-05-21 Sigray, Inc. Detector for X-rays with high spatial and high spectral resolution

Also Published As

Publication number Publication date
EP3602020A1 (fr) 2020-02-05
CN110621986B (zh) 2022-05-17
EP3602020A4 (fr) 2021-07-28
CN110621986A (zh) 2019-12-27

Similar Documents

Publication Publication Date Title
US10416099B2 (en) Method of performing X-ray spectroscopy and X-ray absorption spectrometer system
US10976273B2 (en) X-ray spectrometer system
US10578566B2 (en) X-ray emission spectrometer system
US10295486B2 (en) Detector for X-rays with high spatial and high spectral resolution
US9448190B2 (en) High brightness X-ray absorption spectroscopy system
US9823203B2 (en) X-ray surface analysis and measurement apparatus
US9594036B2 (en) X-ray surface analysis and measurement apparatus
US9570265B1 (en) X-ray fluorescence system with high flux and high flux density
EP3152554B1 (fr) Système de mesure d'absorption des rayons x
US9449781B2 (en) X-ray illuminators with high flux and high flux density
US20190088381A9 (en) X-ray illuminators with high flux and high flux density
US6934359B2 (en) Wavelength dispersive XRF system using focusing optic for excitation and a focusing monochromator for collection
WO2015187219A1 (fr) Système de mesure d'absorption des rayons x
WO2019027761A1 (fr) Système de spectromètre à transmission de rayons x
CN112638261A (zh) 利用滤波的x射线荧光的系统和方法
JP7195341B2 (ja) 波長分散型ｘ線分光計
EP3602020B1 (fr) Procédé de réalisation d'une spectroscopie des rayons x et système de spectromètre d'absorption de rayons x
US6594337B1 (en) X-ray diagnostic system
US5926522A (en) Wavelength dispersive x-ray spectrometer with x-ray collimator optic for increased sensitivity over a wide x-ray energy range
US20200200691A1 (en) Devices and systems for improved collection efficiency and resolution of wavelength dispersive spectrometry
US20060126786A1 (en) Simultaneous measurement of the reflectivity of X-ray with different orders of reflections and apparatus for measurement thereof
Korotkikh Total reflection x‐ray fluorescence spectrometer with parallel primary beam
US20150185168A1 (en) Device for measuring resonant inelastic x-ray scattering of a sample

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191017

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20210629

RIC1 Information provided on ipc code assigned before grant

Ipc: G01N 23/085 20180101AFI20210623BHEP

Ipc: G21K 1/06 20060101ALI20210623BHEP

Ipc: H01J 35/12 20060101ALI20210623BHEP

Ipc: H01J 9/14 20060101ALI20210623BHEP

Ipc: H01J 35/02 20060101ALI20210623BHEP

Ipc: H01J 35/10 20060101ALI20210623BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230202

RIN1 Information on inventor provided before grant (corrected)

Inventor name: STRIPE, BENJAMIN DONALD

Inventor name: LYON, ALAN FRANCIS

Inventor name: SESHADRI, SRIVATSAN

Inventor name: KIRZ, JANOS

Inventor name: LEWIS, SYLVIA JIA YUN

Inventor name: YUN, WENBING

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20230707

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230802

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018063248

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240328

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240328

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240327

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240104

Year of fee payment: 7

Ref country code: GB

Payment date: 20240104

Year of fee payment: 7

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20231227

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1644972

Country of ref document: AT

Kind code of ref document: T

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240327

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240427

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240429

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231227